Mabion b



Patented June 8, 1926.

UNITED STATES 1,588,027 PATENT ol-rlcs.

MARION n.

HOPKINS,- OF ELIZABETH, NEW JERSEY, ASSIGNOR TO STANDARD DE- VELOZPMEN'I. COMPANY, A CORPORATION OF DELAWARE.

NITBATION PROCESS.

Io Drawing.

Thepresent invention relates to the nitration of aliphatic and cyclo-aliphatic or nonbenzenoid compounds, and will be fully understood from the following description thereof. l

In accordance with the present invention, the hydrocarbon to be nitrated is sub]ected to the action of nitric acid, the total amount of which is in .excess of that theoretically necessary for the productionof the mpnonitro derivative, in the presence of aluminum nitrate, which may be employed either in the form of the crystals or the anhydrous compound. The nitric acid is preferably added to the hydrocarbon in the presence of the aluminum nitrate in two or more batches,

although the entire quantity of nitric acid,

may be added at the beginning of the operation, if desired. 'The nitric acid and the hydrocarbon are'heated together in the resence of the aluminum nitrate to or higher, the temperature varying with the boiling point of the hydrocarbon for example, by the use of an oil bath maintained at a temperature 10 to 20 higher than the desired temperature. The vapors passing off from the heated mixture are condensed and the distillate is returned, after separation of the water, intermittently or continuously, as desired, to the reacting mixture. The heating of the mixture is continued under these conditions, for a period of 6 to 9 hours or until the nitric acid becomes substantially inactive. 'At the end of this period the oily products in the reaction cham-v ber are separated from the viscous aluminum nitrate layer and the mono and di-nitro compounds present therein separated by distillation with steam. The mixture of nitrocompounds is found to contain some unchanged hydrocarbon. The proportion of mono-nitro compounds varies, and in the case of octane, for example, isfrom 40 to 60% of the hydrocarbon consumed in the reaction, and the proportion of crude di-nitro compounds from 50 to 60% of the hydrocarbons. The' following specific example illustrates a procedure which may be employed in carrying out the present invention:

About 1400 parts by weight of an octane fraction of petroleum, boiling between and C. is admixed with 1000.parts of 94% aluminum nitrate and 600 parts of 68% nitric acid. The mixture is heated in an oil Application filed March 18, 1922. semi no. 544,949.-

bath maintained at a temperature between 130 C. and C. The mixture of alumi num nitrate and nitric acid form a viscous layer upon which the hydrocarbon oil floats. During the heating a mixture of water, hydrocar on and nitrogen oxide distill off from the mixture and this distillate is condensed, the h drocarbon separated from the aqueous liqui and returned to the reaction mass at intervals. After nine hours heating, the nitric acid becoming substantially inactive, the reaction mass is permitted to cool and 600 parts additional of 68% nitric acid is stirred into the aluminum nitrate layer. The heating is then continued under the same conditions for about six hours. The mixture 'is then allowed to cool. The nitro-compounds admixed with unchanged hydrocarbon separatin nitrate and nitric acid mixture as an oily layer. This oily layer is of itself useful as a solvent, for example, for resinous materials, cellulose derivatives, etc. The oily layer of nitro-compounds is removed and distilled with steam. The unchanged bydrocarbon and the mono-nitro compounds are volatile with steam, and, from 1400 parts .of the oily mixture produced, 950 parts of mixed hydrocarbon and mono-nitro compounds were obtained as a steam distillate. Of this 580 parts is unchanged hydrocarbon and 370 parts crude mono-nitro hydrocarbon. The undistilled residue is crude dinitro compound. The mono-nitro compound is distilled under reduced pressure to effect its purification, and upon examination, is found to be a fairly pure nitro-octane. The di-nitro compound is likewise found to be substantially entirely di-nitro octane.

The process is particularly applicable to the aliphatic and cyclo-aliphatic hydrocarbons having a, boiling point of 115 C. or higher. The nitration of nonane, decane, mixtures of octane and nonane and of nonane and decane, and of gasoline, as well as of cyclo-hexane-and other cyclo aliphatic compounds .has been successfully accomplished by means of the present process. In such reactions the average yield of crude mono-nitro derivatives has been from 40 to 59% of the hydrocarbon consumed, and the yield of crude di-nitro compound from 50 to 60% of the hydrocarbon consumed.

I claim: Y

1. The process of nitrating non-benzenoid from the viscous aluminum ing point in the presence of nitric acid and 'nitro derivatives derivatives. r

4;. The process of nitrating aliphatic hy- -drocarbonsof the gasoline range of boiling hydrocarbons which consists in heating the hydrocarbon to a temperature of at least 115 C. and not substantially above its boil- .ingpoint in the presence of nitric acid and aluminum nitrate.

hydrocarbon to a temperature of at least 115 C. and not substantially above its boilaluminum nitrate, separating. the residual aluminum nitrate and nitric acid from the nitro-compounds" produced and subjecting said nitro-compounds to distillation below theirboiling point to separate the monofrom' the higher nitrated point which consists in heating such hydro.- carbons to a temperature of at least 115 C. and not substantially above its boiling point withat least a molecular proportion of nitric acid in the presence of aluminum nitrate.

5. The process of nitrating non-benzenoid hydrocarbons which consists in heating the hydrocarbon to a temperature of at least 115 C. and not substantially above its boiling point-with less than a molecular proportion of nitric acid in the presence of aluminum nitrate, continuing the reaction until the nitric acid becomes substantially inactive, supplying in the mixture additional nitric acid suflicient to bring the total quantity of nitric acid to at least a molecular propor- 131011 and continuing'the heating of the re action mixture. v

- 6. The process of nitrating aliphatic'hydrocarbons, having a boiling point within the gasoline range of boiling points, which conslsts in heating the hydrocarbon to a temperature of at. least 115 C. and not substantiallyabove its boiling point with less than a molecular proportion of nitric acid in the, presence-of aluminum nitrate, continuing the reaction until the nitric acid becomes substantially inactive, supplying in the mixture additional nitric acid sufiicient to bring the total, quantity of nitric acid to at least a molecular"- proportion and continuing the heating of the reaction mixture.

7. The process of nitrating octane ,whichconsists in heating octane to a temperature I of at least 115 C. with at least a molecular proportion of nitric acid in the presence of aluminum nitrate.

8. As an article of manufacture, a liquid containing octane, mono-nitro-octane and di-nitro-octane.

MARIONB. HOPKINS; 

